CA1146177A - Textile softening and antistatic compounds - Google Patents

Abstract

ABSTRACT
Short chain carbamoyl derivatives of long chain aliphatic amines, wherein the amino nitrogen is attached to a nonterminal methylene group, useful as nonyellowing softening and antistatic agents for laundered fabrics, deter-gent compositions containing an effective softening and antistatic amount of said carbamoyl derivative and a method of softening and protecting fabrics against acquiring static electricity by contacting fabrics with said compositionduring laundering. These compounds provide softening and antistatic protection without reducing optical brightener performance and detergency performance of the detergent composition.

Description

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TEXTILE SOFTENING AND ANTISTATIC COMPOUNDS
This invention relates to novel softening and antistatic agents and detergent compositions to be used in the laundering of fabrics containing said softening and antistatic agent which is a di-substituted urea having the formula:
; RNHCONHR' wherein R is a short alkyl group of 1-6 carbons, and R'is a secondary ali-phatic hydrocarbon chain of 8-22 carbons.
Description of the Prior Art The use of various and diverse chemical materials and particularly cationic qua*ernary ammonium compounds as softeners and antistatic agents or textile products is very well known in the art It is also well known to employ such materials for their antistatic and softening effects during the laundering operation and particularly in the rinse cycle of the laundering process. This technique has been necessitated by the fact that the aforesaid ::
quaternary compounds heretofore employed, being mainly cationic in nature, ~;~ were not compatible with the anionic detergents, one of the major types of i detergents used in the washing cycle.
It is also well known that there is a tendency for laundered articles to yellow or discolor when treated with aforesaid quaternary compounds.
Another disadvantage associated with the use of said cationlc agents in the laundering o Eabrics therewith is its interference with the deposition on the fabrics of optical brightener, thereby reducing optical brightener performance of a detergent composition containing said optical brightener.
Still another disadvantage of the cationic quaternary ammonium anti-static softener i5 its interference with the cleaning properties of the detergent by reducing the soil removal cffected by the detergent, resulting in - 1 - ~ ' ' ~k ~, . ~ . . . . ~ , ., ,, - .

decreased washing effectiveness. The presence of the anionic detergent material substantially negates the fabric softening properties of the ca-tionic quaternary ammonium compounds as well as counteracts the antistatic activity possessed by said quaternary compounds.
Accordingly~ substituted urea compounds such as methylol urea has been found useful in the treatment of fabrics such as in textile finishing compositions, as disclosed in United States Patent No. 3,651,139 to Feinauer et al; and N-octadecyl-urea formaldehyde has utility as ~extile softening agentsas disclosed in United States Patent No. 3,671,308 to Diery et al.
Similarly, substituted urea compounds have been used in the treatment of textile materials to provide a permanent softening effect as disclosed in United States Patent No. 2,30~,113 to rlorgan et al; and fabric softener com-positions containing diphenyl urea derivatives as stabili~ers for quaternary ammonium fabric softeners is disclosed in United States Patent No. 3,216,9~ to Fredrickson, and the reaction product of urea with a cationic-containing com-:: pound such as a quaternary ammonium compound, a primary, secondary, or tertiary .: amine having at least one long alkyl chain, is disclosed in United States Patent No. 3,256,180 to Weiss~
: Urea~ monobutyl urea, dibutyl urea, phenyl urea and acetyl methyl urea have been used in soap bars as disclosed in United States Patent No.

2,37~,187 to Flett; and substituted urea compounds with one or more alkyl groupscontaining 1-~ carbons have been used in hair preparations as disclosed in United States Patent No. 3,1~9,0~2 to llabicht et al.
Low foaming cleaning compositions which may contain an alkylated urea substituted by wo long alkyl chains, at least one on each N, whi.ch may be strai.ght-chain or branched is disclosed in United States Patent No. 3,691,0S2 to Stimberg et al; and bleach-stable fabric detergent and/or softening composi-~_ .~. . .

; . . . : .

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~16~7 tions containing a substituted urea having the formula:
RNHCONH(cH2)nNH2 wherein R is an alkyl group containing 2-18 carbons and n is 2-12 as the soften-ing agent, is disclosed in United States Patent No. 3,965,015 to ~auman.
Dialkyl urea compounds having a short alkyl group on one nitrogen and a long alkyl chain on the other nitrogen have been used in detergent com-positions to enhance detergency and foaming as disclosed in United States PatentNo. 2,708,183 to Ross. United States Patent No. 3,1~0,763 to Schleede et al ~; also discloses dlsubstituted urea compounds such as N,N' dimethyl urea and N,N' didodecyl urea useful in the antistatic finishing of plastics.
llowever, none of aforesaid prior art substituted urea compounds or , carbamoyl derivatives are short chain carbamoyl derivatives of long chain aliphatic amines, wherein ~he amino nitrogen is attached to a non-terminal methy-lene group; said compounds possessing both softening and antistatic properties.
~ Summary of Invention .~ _ ~; It has now been discovered that the dialkyl urea compounds oE this invention provide antistatic properties and fabric softening benefits, without causing fabric yellowing, do not interfere with optical brightener action and are compatible with detergents.
Accordingly, it is a primary object of the instant invention to protect fabrics against acquiring static-electrical charge during machine dryingsubsequent to the laundering.
Another object of the instant invention is to provide such protec-tion in conj~mction with conventional detergent compositions during the home ~`
laulldering process.
, A further object of the instant invention is to provide softening ii ~' and antistatic protection without yellowing and without reducing optical .:1 .

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brightener perEormance.
Still a further object of instant invention is to provide a softening and antistatic composltion which may be employed in conjunction with detergents and other cleaning, brightening and laundering additives in a single step laundering operation.
Accordingly, the instant invention relates to softening and anti-static laundering compositions compatible with detergents; and to novel short chain carbamoyl derivatives of long chain aliphatic amines, wherein the amino nitrogen is attached to a non-terminal or internal methylene group, represented by the structural formula:
RNHCONHR' ~
whereln R is a short alkyl chain containing 1-6 carbons, and R' is a secondary aliphatic hydrocarbon chain containing 8-22 carbons; and to the process for mlparting softening and antistatic properties to fabrics which consists in treating fabrics with a composition containing a dialkyl urea substituted on one nitrogen by a secondary long chain aliphatic hydrocarbon and substituted on the other nitrogen by a short alkyl radlcal. More speciEically, antlstatic propertles are imparted to fabrics by laundering the fabrics in a composition containing a detergent, pre~erably anionic or non-ionic, the above defined di-;alkyI urea compound and other ingredients such as phosphate or non-phosphate builders, optical brighteners, enzymes, bleaches, and other conventional additives.
The instant novel dialkyl urea compo~mds substituted OTI one nitrogen atom with a secondary long aliphatic chain containing 8-22 carbons and sub-stituted on the other nitrogen with a short alkyl radical containing 1-6 carbons and preferably 1-4 carbons, reduces or prevents the generation of static elec-tricity on cotton and synthetic fabrics during laundering. These antistatic : ' :
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properties can be imparted to fabrics by laundering in a detergent composition containing said dialkyl urea compounds which are completely compatible with anionic, nonionic, cationic and amphoteric detergents. This same treatment has been found to additionally confer a soft hand on cotton fabrics and to enhance the detergency action of the detergent composition. These beneficial effects are achieved without yellowing or discoloration of the fabrics and without inter-ference with the action of optical brighteners that may be present in the deter-gent composition.
The dialkyl ureas may be single homologs or mixtures thereof. They ~; 10 may also be mixtures of isomers in which the RNHCONH- group is a~tached to any interior methylene group of the chain, with terminal substitution being preclud-ed. Substitution may predominantly be at the more centrally located methylenes of the chain, at the central methylene, at the beta methylene, and so forth.
The dialkyl urea compo~mds o instant invention can generally be prepared by the conventional reaction o an amine with an isocyanate. ~or ex-:
`~ ample, a solution o a long chain amine in methylene chloride may be treated with excess or equimolar quantities of a Cl-C6 alkyl isocyanate. The product, isolat-~:
~ ed as a viscous oil or waxy solid, may be used as is or purified by distilling , ~ .
out~low boiling ractions.
~ore speciflcally, instant novel dialkyl urea compounds are prepared ' from known starting materials by reacting an alkyl isocyanate;such as methyl- or ethyl- or~propyl- or butyl-isocyanate (RNC0) with a primary aliphatic amine containing 8-22 carbons wherein the amino functional group is attached to an interior carbon atom of the hydrocarbon chain. Beta amines~ manufactured by the Armak Company, which are long chain primary amines, wherein the amino f~mctional .
group is attached to an interior carbon atom, predominantly at the beta carbon atom, are suitable reactants. The reaction may be conducted at room temperature ,, !' ,~
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or under re:Elux conditions. A150J the reaction may be conducted in the presence of any non-reactive organic solveilt such as me~hylene chloride, methyl or ethyl ether, benzeneJ chloroform or the like. The product is preferably isolated by by evaporating in vacuum. Ihe resultant dialkyl ureas which are usually made from mixtures of aminesJ are liquids, oils or solids.
The beta amines useful as a reactan~ herein may also be prepared by utilizing the Ritter reaction of converting ~-olefins containing C~-C22 into internally substituted amines by reacting with sodium cyanide in the presence of a strong acid such as H2S04, hydroly~ing the resultant formamide with hydro-bromic acid into the beta amine, which is processed by neutralizing with sodium hydroxide, washing with water and NaHC03~ drying over Na2S0~ and evaporating in vacuum and purifying by distillation.
The following examples illustrate the manner in which compounds of this invention are prepared, but is not limited thereto~

Preparation of the methyl carbamoyl derivative of the beta amine, C113 (CH2312-17 C, ~INH2 CH3(cH2)l2-l7-cHNHcoNHcH3 CH
To a solution of 165 g of said beta amine (Armeen* L-15 -from the Armak Company) in 500 ml methylene chlor:ide heated on a steam bath to a reflux temperature, was slowly added from a dropping :Eumlel, 36 ml methyl isocyanate in 70 ml methylene cllloride. The temperature was maintained at a gentle reflux :~ during said addition which took 55 minutes. The mixture was refluxed for an ; additional hour and evaporated in vacuum to 179 g of a dark yellow oil.

*Trade mark , ~6~7 Preparation of the methyl carbamoyl derivative of the beta amine, CII3~CH2)8_ll CHN 2 3~ 2)8-11 CON 3 CH
To a solution of 112 g ~0.5 mole) of above beta amine ~Armeen L-ll*
from the Armak Company) in 300 ml methylene chloride heated to a reflux tempera-ture was slowly added with gentle reflux 35 ml ~0.6 mole) methyl isocyanate.
1- Addition took one hour. The reaction mixture was refluxed for one hour longer, then evaporated in vacuum. After distilling out IO g low boiling material at 70-100C, 121 g topped oil was recovered (purified).
The process described in the above examples may be varied by using other non-reactive organic solvents such as ether, benzene, chloroform, etc..

I Preparation of methyl carbamoyl derivative of beta dodecylamine:

I~ CH3 - ~ 10 21 3 N-beta dodecyl-N'-methylurea "~ ~
; 32 g ~0.166 mole) beta dodecylamine in 60 ml methylene chloride was heated to reflux on the portable steam bath and then shut off. 11.9 ml methyl isocyanate was added under gentle reflux in 10-12 minutes and refluxed one hour longer. The reaction mixture was evaporated in vacuum and a yield o-f 39 g of a ; white solid was obtained. A 2.0066 g sample, titratecl with 0.05N HCl, used 0.05 ml at end pOiIIt. This shows completeness of reaction, since a negligible amount of amine is left unreacted.
~, ~EXAMPLE 4 Preparation of methyl carbamoyl derivative of beta tetradecylamine:
*Trade mark Cl 21125CHNHCONHCH3 N-beta tetradecyl-N'-methylurea 46 g (0.19 mole) of the beta amine in 60 ml methylene chloride was heated to reflux on a steam bath. 13.7 ml methyl isocyanate in 15 ml methylen0 chl~ride was added dropwise, maintaining a gentle reflux, over a per-iod of 10 minutes. The reaction mixture was refluxed one additional hour and then evaporated in vacuum, yielding 53.8 g white solid.

Preparation o methyl carbamoyl derivative of beta hexadecylamine:

N-beta hexadecyl-Ni-methylurea ~ ~ 38.6 g ~0.135 mole) beta-hexadecylamine in 60 ml methylene chloride `~ was reacted with 9.6 ml methyl isocyanate in 15 ml methylene chloride in accord-, .
ance with the procedure in Example 4, yielding a white solid reaction product.
Other N,N' substituted urea antistatic agents in accordance with instant invention can be prepared by using other alkyl isocyanates such as ethyl, propyl, butyl, pentyi and hexyl isocyanate. Similarly, other long chain ali-phatic prlmary amines wherein the amino functional group is attached to any inner carbon atom may be used in the preparation of instant dialkyl urea anti-static and softening agents,~such as octyl, nonyl, decyl, heptadecyl~ octadecyl,~
nonadecyl eicosanyl, amine, etc. and mixtures thereof. Primary amines where the amino group is attached to the terminal carbons~ such as dodecylamine, hexadecylamine, octadecylamine, cocoamine and the like yield dialkyl ureas with very limited effect on static and fabric softening.
Accordingly, it has been found that the substituents on the nitrogen atoms of the urea effective as softening and antistatic agents are one short 46~ ~7 alkyl chain containing 1-6 carbons, and one secondary long aliphatic chain con-taining 8-22 carbons, one on each nitrogen.
The antistatic compoullds of this invention may be used in conjunction with detergents which include anionic detergents such as alkylbenzene-sulfonic acid and its salts, e.g. compounds of the formula alkyl-phenyl-SO3 -M~ wherein alkyl is an alkyl radical of C8 to C22 and preferably C10 to C18 and ~ is hydrogen or an alkali metal, which compounds comprise a well known class of anionic detergents and include sodium dodecylbenzene sulfonate, potassium dodecyl-benzenesulfonate, sodium laurylbenzenesulfonate, sodium cetylbenzenesulfonate.
Others include paraffin sulfonates, alkyl sulfates, alcohol ether sulfates, ole-fin sulfonates and the alkylphenolethoxylate sulfates ~e.g., sodium dinonyl-phenoxynonaethoxyethanol sulfate, sodlum dodecylhexadecaethoxyethanol sulfate), ., .
and other equivalent water-soluble salts, particularly of the alkali metal .~ .
series.
;~ ~ Among the above-noted alkylbenzene-swlfonic acid and salts thereof, the preferred compounds include those which are biodegradable and which are par-~:
ticularly characterized by a linear alkyl substituent of from C10 to C22 and ..
preferably from C12 to C15. It is, of course, understood that the carbon chain length represents, in general, an average chain length since the method for producing such products usually employs alkylating reagents of mixed chain length. It is clear, however, that substantially pure olefins as well as alky-lating compounds used in other techniques can and do give alkylated benzene sul-tonates wherein the alkyl moiety is substantially ti.e., at least 99%) of one chain length, i.e., C12, C13, Cl~, or C15. The linear alkyl benzene sulfonates are further characterized by the position of the benzene ring in the linear alkyl chain with any of the position isomers ~i.e., alpha to omega) being operable and contemplated.

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~6~77 In addition to the benzene sulfonates one may also employ the lower alkyl (Cl to C~) analogs of benzene such as toluene, xylene~ the trimethyl benzenes, ethyl benzene~ isopropyl benzene and -the like. The sulfonates are generally employed in the water soluble salt form which include as the cationJ
the alkali metals, ammonium and lower amine, and alkanolamine cations.
Examples of suitable linear alkyl ben~ene sulfonates include:
sodium n-decyl benzene sulfonate sodium n-dodecyl benzene sulfonate sodium n-tetradecyl benzene sulfonate sodium n-pentadecyl benzene sulfonate sodium n-hexadecyl benzene sul:Eonate - and the corresponding lower alkyl substituted homologues of benzene as well as the salts of the cations previously referred to. Mixtures of these sulfonates "~
may~ of course, also be used with mixtures which may include compounds wherein the linear alkyl chain is smaller or larger than indicated herein provided that the average chain length in the mixture conforms to the specific requirements f C10 to C22.
The linear paraffin sulfonates are also a well-known group of com-pounds and include water-soluble salts ~alkali metal, amine, alkanolamine) and ammonium) of:
l-decane sulfonic acid l-dodecane sulfonic acid l-tridecane sul:~onic acid l-tetradecane sulfonic acid l-pentadecane sulfonic acid l-hexadecane sulfoni.c acid as well as the other position isomers of the sulfonic acid group.

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In addition to the paraffin sulfonates illustrated above, others with the general range of C10 to C22 alkyls may be used, with the most preferable range being from C12 to C20.
The linear alkyl sulfates which are contemplaked in this invention comprise the rang~ of C10 to C20. Specific examples include sodium n-decyl sul-fate; sodium n-dodecyl sulfate; sodium n-hexadecyl sulEate; sodium n-heptadecyl sulfate; sodium n-octadecyl sulfate; and the ethoxylated (1 to 100 moles ethylene oxide) derivatives; and, of course, the other water-soluble salt-form-ing cations mentioned above.
Included in the group of anionic detergents, which have been describ- -ed above as suitable in the present invention, are the olefin sulfates, including long chain alkene sulfonates, long chain hydroxyalkane sulfonates, as well as disulfonates. Examples of suitable olefin sulfonates, which are merely illus-l ; trative of the general class, are sodium dodecenyl-l sulfonate, sodium tetra--;` decelyl-l sulfonate, sodium hexadecenyl-l sulonate, and sodlum octadecenyl-l ~ sulfonate.
:`' Also useful in conjunction with instant antistatic and softening dialkyl ureas are non-ionic detergents which are commercially known, such as ~: -`~ alkylaryl polyglycol detergents such as alkylphenol-alkylene oxide and preferably ethylene oxide condensates ~2-200 moles ethylene oxide), e.g., p-isooctyl phenol-:, polyethylene oxide (10 ethylene oxide units), long chain alcohol-ethylene oxide ,, .
condensation products (2-200 moles ethylene oxide}, e.g., dodecyl alcohol-polyethylene oxides having 4-16 ethylene oxide units per molecule, polyglycerol monolaurate, glycol dioleate, sorbitan monolaurate, sorbitan monostearate, sorbitan monopalmitate, sorbitan monooleate, sorbitan sesquioleate, the con-densation products of ethylene oxide with sorbitan esters of long chain fatty acids (Tweens*),alkylolamides, amine oxides, phosphine oxides, etc *Trade mark - 11 -, , :

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In addition to the anionic and nonionic detergents which may be employed in conjunction with the antistatic agents of instant invention, cationic, ampholytic, and ~witterlonic compounds have also been found to be useful. Re-presentative of those compounds which may be employed in conjunction with the instant fabric antistatic compounds include quaternary ammonium compounds, e.g.,distearyl dimethyl ammonium chloride, cetyl trimethyl ammonium bromide, sodium 3-dodecylamino propionate, fatty carbamides, etc The composition of the instant invention may also include, in addi-tion to instant antistatic compounds and conventional anionic, cationic, and nonionic detergents, builders, brighteners, hydrotropes, germicides, soil sus-pending agents, anti-redisposition agentsl antioxidants, bleaches, coloring ; materials ~dyes and pigments~, perfumes, water-soluble alcohols, foam boosters, non-detergent alkali metal ben~ene sulfonates, etc The builder is, generally~ a water-soluble, inorganic salt which may be a neutral salt, e.g., sodium sulfate or an alkaline builder salt such as phosphates, silicates, bicarbonates, carbonates, citrates and borates. The :
preferred builders are those characteri~ed as condensed phosphates such as poly-phosphates and pyrophosphates and alkali citrates. Specific examples of alkaline: salts are: tetrasodium pyrophosphate, pentasodium tripolyphosphate (either ~20 Phasè I or Phase II), sodium hexametaphosphate, and the corresponding potassium salts of these compounds, sodium and potassium silicates, e.g., sodium meta-silicate and other silicates ~e.g., Na20; 1.6-3SiO2), sodium carbonate, potassium carbonate and sodium and potassium bicarbonate, sodium citrate and potassium citrate. Other salts may also be used wherein the compo~mds are water-soluble including the general class of alkali metals, alkaline earth metals, amine, alkanolamine, and ammonium salts. Other bui:lders which are salts of organic acids may also be used, and in particular the water-soluble ~alkali metal, ' ammonium substituted ammoniwn and a.mine) salts of aminopolycarboxylic acids such as:
ethylene diamine tetra-acetic acid nitrilo triacetic acid di.ethylene triamine pentaacetic acid N-~2-hydroxyethyl)-ethylene diamine triacetic acid 2-hydroxyethyl-iminodiacetic acid 1,2-diaminocyclohexane diacetic acid and the like. Water-insoluble builders having cation-exchange properties may be used also, such as the sodium alumino-silicates, for example Zeolite A~ which ; may be used alone or in combination with other builders such as sodium tripoly-- phosphate.
In addition to the above ingredients one may, as previously delineat-. ed, employ hydrotropcs in connection with the composition of the instant invention. The useful hydrotropes include such:compounds as sodium xylene sul-fonate, potassium xylene sulfonate, sodium and potassium toluene sulfonates, and':1 .~ the position isomers thereof, ethyl benzene sulfonate, cumene sulfonates, and : the like.

In additlon to compositions comprising the novel dialkyl urea anti-:20 ~ static and softening agents of the instant in~entlon in combination with deter-; gent and conventional l.aundering additives, it is noted that said antistatic ~ ~ .
agents may in addition be formulated in suitable vehicles for addition to the laundering cycle with the concomitant addition of detergent materials. In connection therewith said dialkyl urea may be solubilized and/or dispersed by ~:~ convontional techniques utilizing alcohols, ether alcohols~ hydrotropic solutions, .~ glycols, and the like. Furthermore, it is noted that said antistatic agents may also be absorbed onto suitable salts and/or other carriers for addition to ~: ~
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the laundering cycle such as, for example, phosphates, boraxJ silicates, sodium sulfonate, clays~ starch, and the li]ce. A preferred carrier is a carbonate base bead comprising 49.04 parts sodium bicarbonate, 10.67 par-ts sodium carbonate, 17.00 parts silicate solids, 0.015 parts xylene red color and 6.00 parts water.
The following Example specifically illustrates a method of dispers-ing the dialkyl ureas on carbonate base beads. However~ it is merely illus-trative thereof and it is not limited thereto.

Base Bead_Conlposition Ingredients _arts ~3 49.0~
; Na2C03 10.67 ~ Silicate Solids 17.00 :-; Xylene Red ~olor 0.015 H20 6~00 ~: 10 g of warm bead composition which was preheated on a steam bath was added to 5 g melted dialkyl urea of Example 1 on a steam bath and stirred ~: vigorously. The mixture was substantially free flowing.
: The amount of dialkyl urea utilized in connection with detergent ::
compositions is generally considered to be a relatively small proportion as :~
compared to the weight of the active ingredients therein. It is noted, however~
that one need only employ an effective amount of said dialkyl urea which in fact produces the desired antistatic and softening action on fabrics. It is pre-ferred that sa.id urea be present i.n an amount of from about 2% to about 25%, and preEerably 5% to 20~, of the total ingredients present in the detergent composition on a weight basis.
The composition of the ins~ant invention may be employed in either : :

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particulate, liquid, tablet, or any other conventional form. Moreover, as notedabove~ the novel dialkyl ureas as disclosed herein may be employed as antistatic and softening fabric agents by being applied to textile materials during the washing process, with the concomitant addition of detergent materials thereto, or used as a presoak product prior to washing or as a rinse cycle additive after the wash cycle.
The laundering and presoak composition of instant invention will now be illustrated by the following more detailed examples thereof. It is noted, however, that these compositions are merely illustrative and it is not limited thereto.
Examples 7 a, b, c, d, e Non-phos~late anionic detergent Ingredient %
Sodium Dodecyl ben~enesulfonate 23 Sodium carbonate 20 Sodium silicate (1:2.~) 15 Soap (Sodium Coco-Tallow 80:20) 2 Nonionic detergent*
Bora~ 3 Sodiumcarboxymethylcellulose 1 Optical Brightener .5 Calcined aluminum sillcate Sodium sulfate 30.5 ; Water 3 100.0 *Fatty alcohol ~C12 15) with average of 7 moles ethylene oxide This composition is spray-dried to produce a powder. To 100 g of this formulation is added 2-10 g dialkyl tlrea antistatic and softening agent:

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~L~ 7 7 a. N-beta dodecyl-l~'-methylurea b. Ethyl carbamoyl derivative of Armeen L-15 c. CH3~CH2)8 11 Ci~HCONHCH3 (Methyl carbamoyl derlvative CH3 of Armeen L-ll) d. CH3(CH2)12 17 CHNHCONHCH3 ~ethyl carbamoyl ,-lerivative CH3 of Armeen L-15) e. Propyl carbamoyl derivative of Armeen L-15 Examples 8 a, b, c, d, e Phosphate-built Anionic Detergent Ingredient %
Sodium Tridecyl benzenesulfonate 15 Nonionic detergent* 5 Sodium silicate (1:2.4) 10.5 Sodlum tripolyphosphate 33 Sodium carbonate 5 Sodium sulfate 24 Sodium Carboxymethylcellulose .25 ; Optical Brighteners .5 - Borax 1.0 Perfume .15 Water 10.1 100.0 *Fatty alcohol (C12 15) condensed with average of 7 moles ethylene oxide.
This composition is also spray-dried to produce a powder.
- To this composition is added 2-10 g of the dialkyl urea antistatic and softening agent:
i a. methyl carbamoyl derivative of beta-tetradecylamine of Example

4.

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b. methyl carbamoyl derivative of beta-}lexadeeyl~mine of Example 5.
c. CH3(CH2)8_11 ,CilNH 3 d. CH3(CH2)12-17 , N 3 e. ethyl carbamoyl derivative of Armeen L-15 EXAMPLE 9 a, b, c, d, e Built Nonionic Detergent In~redient %
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Ethoxylated alcohol* 19 :
Sodium tripolyphosphate 60 Sodium silicate ~1:2.4) 10 Optical Brighteners 2 ;~ Enzyme (Proteolytic) 1.5 ~ ~ Perfume and Color 0.35 ; P~loisture 7.15 ~'~ ' 100. 00 ~"' :
~-~ *Fatty alcohol (C12 13) condensed with an average of 6.5 moles ethylene oxide.

To 40 g of this formulation which lS in the form of a powder, is added 2-10 g of fabric antistatic soften m g~ agent:

a. N-(C18 secondary linear hydrocarbon)-N'-methylurea b. N-(C20 secondary linear hydrocarbon)-N'-methylurea c. CH3(C~12)8 11 C~INHCN~IC~13 .
: C~13 ;~ d- CH3(CH2~12-17 C,HN~ICON~ICH3 ~ e- (C5Hl1)2 CHNHCONHCH3 ; ~:
~ - 17 -~ , , ~4~L7~

Presoak Product Ingredient Parts .
Sodium Linear tridecylbenzene sulfonate 6.3 Sodium silicate 8.3 Sodium tripolyphosphate 41.7 Sodium sulfate 35.4 Water 8.3 ~ 6 g of the dialkyl urea of Example 1 and 48 g of the above presoak ; 10 formulation were added to a GE washer at 120F and agitated to dissolve.
Swatches of 4 fabrics, cotton terry, dacron*~ nylon and dacron*/cotton were : added, agitated for 1 minute and let soak overnight. In the morning, the water ~`
was spun out and 100 g of a phosphate-built anionic detergent was run through - the regular wash cycle at 120~F. Another run was made with the same dialkyl .~
urea, the detergent and the presoak formulation added at the same time to the - washer, and a control was run with the detergent and presoak product alone.
~ The results given in Table I, clearly show the antistatic and softening activity ;~ of instant ureas in presoak formulations as well as in detergent composttions.
TABLE I
20~ ~ Material~ Static (1) Softness (2) Example l~urea, presoak0.1 kV 6 Example 1 urea, no presoa]c 0 Control 22 ; tl} Sum of the absolute values of surface charges of the 4 ~abrics Oll removal from the dryer.
~2) Subjective reading on a scale of 1 to lO; higher values are softer.
.
The presence of the methyl carbamoyl derivative of Armeen L-15*
*Trade~mark i, 6~7 boosted detergency of the composition and showed insignificant yellowing and brightener effects.
Utility of the dialkyl ureas in reducing static electricity and en-hancing softness properties of fabrics during the laundering process, without yellowing or depressing brightening was shown in a test run in GE washers ~18 gal. water) at 120F with a mixed clean fabric load (cotton terry, dacron*
double knit, Banlon* nylon, dacron*/cotton 65/35) and soiled swatches (Test Fabrics nylon, Test Fabrics cotton, Scientific Services clay on cotton, Scientlfic Services clay on dacron*/cotton, EMPA cloth), and twnble dried for 45 minutes. In each case 5 g of the test material was added to the washer simultaneously with 40 g of the formulation of Example 9 or as indicated.
TABLE II
Amide Static Value Softness ~ .:
~d~ 1. None 13.7 kV

2. L-15 methyl urea 0 8 3. L-15 ethyl urea 0 5 ,. ~
~ 4. L-15 propyl urea 0.1 6 :

5. ~10 g base beads of Example 6 5.6

6. 5 g L-15 methyl urea* 0.2 8

7. 5 g beta C12 methyl urea* 0.2 6 : ~, .
; ~ ~ 8. 5 g beta C14 methyl urea* ~ 0.7 9. 5 g beta C16 methyl urea* 5.0 4 10. 5 g beta C18 methyl urea* 5.8 5 11. 5 g beta C20 methyl urea* 5.6 5 12. 5 g beta C22 methyl urea* 5.5 4 * The dialkyl urea is dispsersed in 10 g base beads as shown in Example 6.

Using concentrations from 7.5 to 240 ppm, the compounds of this invention were found to have no significant effect on overall detergency of the *Trade mark ~: - 19 - ~, :~:
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6~7 soiled swatches, to cause no loss in brightener efficiency, and to cause no significant yellowing of nylon or cot~on in contrast to quaternary ammonium compounds similarly tested which were deficient in all these areas. The re-duction in static electricity on the tu~ble dried fabrics was found to be concentration dependent with over 90% effectiveness at levels of 60 ppm or more in contrast to an average reduction of 30% for a quaternary ammonium antistatic agent which did not improve with increasing concentration.
Comparative results with dialkyl ureas wherein the long chain sub-stituent on the nitrogen is a primary hydrocarbon radical, not embraced by instant invention, show their inability ~o soften fabrics and reduce static electricity generated during the washing and drying of mixed fabric loads.
The efficiency of the methyl carbamoyl derivative of ~rmeen 1.-15*
-15 methyl urea) in comparison with the derivative of cocoamine (coco methyl :
~ urea) is shown by tests conducted in GE washers (18 gal. water) at 120F with a :
mixed clean fabric load of cotton/polyester terry, dacron* double knit, Banlon*
nylon and 65% dacron*/cotton, wherein the test material was added simultaneously with 40 g of the phosphate-built non ionic detergent of Example 9.

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: TABLE III
L-15 methyl urea coco methyl urea Amount ~per wash (g) Staticsoftness Static Softness : 0 24.3 1 24.3 0.5 15.5 1 15.6 3 1 6.8 3 20.6 2 0.5 6 19.6 5 0.8 9 20.6 3 .
6 0.1 10 10.5 4

8 0.05 10 9.1 4 12 0.0 10 7.~ 3 This table clearly shows that the carbamoyl derivatives of a :: terminally substituted long chain ami.ne is relatively ineffecti.ve as an anti-~: stat.ic and softening agent.
Table IV utllizes 5 g of dialkyl urea with 100 g of the anionic `
de*ergents both phosph~ate-containing and no phosphate-containing as shown in `~ Examples 8 and 7:respectively or as otherwise indicated.
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, 6~L~7 TABLE IV
__ Detergent composition Urea Softness at.ion v_lue 1. Example 8 - 1 23.0 2. Example 8 L-15 methyl urea 8 0.1 3. Example 7 - 1 15.5 4. Example 7 L-15 methyl urea 6 0 5. Example 7 (9Og) CH3 1 0.3 CgHlgCH-NHCONLlCH3 *

6. Example 9 ~40 g~+l5g - 1 27.0 base beads o-~ Example 6 7. Example 9 L-15 methyl urea* 6 0 8. Example 8 ~ 15g - 1 21.0 beads of Example 6

9. Example 8 L-1.5 methyl urea* 8 0.15

10. Example 7 ~ 15g base beads of Example 6 - 1 16.8

11. Example 7 L-15 methyl urea* 10 0

12. Example 7 (90 g) L-ll methyl urea* 5 0.05

13. Example 7 (90 g~ L-ll methyl urea~L-15 8 0 methyl urea ~1:1)*
*5 g dispersed in 10 g base beads o:E Example 6.
The ability o~ a dialkyl urea with a secondary long alkyl chain sub-stituent to reduce static electricity and provide fabric softening in the presence of both anionic and non-ionic detergents~ either phosphate--built or non phosphate-containing is clearly shown in the above Examples.
The addition of bleach during the wash cycle does not adversely - 22 - `:

L6~

affect the static suppression properties and the softening properties of the ureas of instant invention, nor is there any interference by these antistatic and softening agents with the bleaching action.
In connection with the subject compositions~ it is noted that in built detergents, the organic cleaning agent, i.e., the anionicJ nonionic, etc., compound may comprise from about 5% to upwards of 75% by weight of the total formulation and usually varies from 5% to 35% by weight. In liquid compositions, the amount of water used is relatively high in order to obtain pourable and .
generally stable systems. Ln these, total solids may vary from a few percent, i.e., 2-10%, upwards of about 50-60% with the organic detergent present, usual-ly in amounts from about 2-25% and preferably 5-15%. In so]id formulation, .e., powder, etc., total solids may run as high as 90% or more and here khe organic detergent may be used ak the high concentrations above indicated, but :
usually the range is 5-25%. The second major component of the built or heavy "
duty liquids, and this is true of the solid (i.e., powdered or kableted kypes) formulations also, is khe alkaline builder salt, and the amount thereof again may vary considerably, e.g., from 5-75% of the total composition. In solid formulations, larger percentages are generally employed, e.g., 15-50%, whereas n the liquid types, the salts are used in lesser amounts, e.g., 5-25% by ~; 20 welght of the total composition.
It is understood that the foregoing detailed description is given merely by way of illustration and that variations may be made therein without departing from the spirit Oe the inventlon. The "Abstract" given above is merely for the convenience of technical searchers and is not to be given any ~ weight with respect to the scope of the invention.
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Claims (18)

1. THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
   PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
   
   l. Dialkyl urea antistatic and softening agents substituted on both nitrogen atoms and having the formula:
   RNHCONHR' wherein R is a short alkyl group of 1-6 carbons, and R' is a secondary aliphatic hydrocarbon chain of 8-22 carbons.
2. 2. A compound in accordance with Claim l, which is a methyl carbamoyl derivative of a long chain aliphatic amine, wherein the amino nitrogen is attached to a non-terminal methylene group.
3. 3. A compound in accordance with Claim 2, which has the formula:
   
   
4. 4. A compound in accordance with Claim 1, which has the formula
5. 5. A compound in accordance with Claim 2, which is a methyl carbamoyl derivative of beta dodecylamine.
6. 6. A compound in accordance with Claim 2, which has the formula:
   
   
7. 7. A non-yellowing antistatic and softening composition for laundering fabrics comprising an effective antistatic and softening amount of the dialkyl urea antistatic and softening agent defined in Claim 1, and a detergent selected from the group consisting of anionic, nonionic, cationic, ampholytic and zwitterionic detergent materials,
8. 8. A non-yellowing antistatic composition for laundering fabrics com-prising about 2-25% by weight of the dialkyl urea antistatic and softening agent defined in Claim 1, and a non ionic detergent.
9. 9. The composition of Claim 8, additionally comprising optical brighten-ers and builders.
10. 10. The composition of Claim 7, wherein the detergent is anionic and the antistatic agent constitutes about 2-25% by weight of the composition.
11. 11. The composition of Claim 10, additionally comprising optical brighteners and builders.
12. 12. The composition of Claim 7, wherein the urea antistatic and soften-ing agent is absorbed on a carbonate base bead carrier comprising sodium bi-carbonate, sodium carbonate and silicate solids.
13. 13. A method of protecting fabrics against acquiring static electricity and simultaneously imparting softness thereto during the laundering process comprising contacting fabrics with the composition of Claim 7.
14. 14. A process of imparting both antistatic and softening properties to fabrics which consists in treating fabrics with a composition containing an antistatic and softening amount of the compound defined in Claim 1.
15. 15. The method of Claim 14, which consists in laundering the fabrics in a composition comprising a detergent and the antistatic and softening com-pound defined in Claim 1.
16. 16. The method of Claim 14, wherein the antistatic and softening agent is added during the rinse cycle after the wash cycle.
17. 17. The method of Claim 14, wherein the antistatic and softening agent is added to a presoak composition prior to the wash cycle.
18. 18. The method of Claim 14, wherein the antistatic and softening agent is added during the wash cycle.